AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

...........................1............................................................................................1 How often should the concentration be determined?............3 The Cautious start .....................8 2............................................................3 Stirring speed and dispersion of the volumetric KF titrant......................................................16 3................................11 2..........................4..................7 2....4...........................................5 Karl Fischer reagents with ethanol ....................2..............................................3................................7 2.........6 Dissolving capacity of the solvent ...............6 General recommendations .........................................................................................................4 Cleaning the coulometric KF titration cell......................1.......1....................................1....................1 Principle of bipotentiometric indication ..9 2............................34 4.............................1.............................................................................................................33 4.....14 3................4 1.................................7 2............................................................................................13 3............METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration ....................................4...........................................5 Control paramaters in the coulometric KF Analysis ....................4 Special reagents for aldehydes and ketones.............................1.............11 2..................................................................1 An historic overview ........................3 Pyridine-containing reagents .........................8 2.......3 Concentration determination with Water Standard 10.....................2 The drift ..........2........................................37 4..........33 4....6...................................................20 3...3.2 The Karl Fischer chemical reaction ......................27 4........................5 Limitations for the use of the cell without diaphragm.................2...2 Working with the coulometric KF instruments ...........1 One-component KF reagent ....................................29 4......................................................1 The Control Band ..2...................................................................................................39 1 ......9 2...................................2.....1 Indication ........................................26 4.............5 Application tips ...36 4..........................2 Coulometric KF analysis..........16 3.................................................................3 Iodine generation..................29 4...................26 4..............................................................................2........................18 3.10 2.....................................4 Polarization current and end point......19 3....4................................................................................................................................................1..........6 Termination parameters for both coulometric and volumetric KF titration....1...........................6 2 Volumetric and Coulometric Karl Fischer Analyses ............18 3..................1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration ........................................2 End point and polarization current.............................................................................22 3..3.................12 3 Titration control and end point determination.....................................4 1.................................................................3 Secure draining and filling of the titration cell: SOLVENT MANAGER.....................35 4..4 Control parameters in the volumetric KF titration .................................2 Stoichiometry of the coulometric KF rection .2 When do you have to replace the electrolyte? .......................2 Reaction rate .....................................................3 Consequences for practical applications..........3.......32 4.......3.................................................................................................5 The solvent.............5 Cleaning the measuring electrode ...........................4............................1 Volumetric KF reagents.....................................9 2...2 Concentration determination with di-sodium tartrate dihydrate.............................................................28 4.............................................................26 4......................................................................................................13 3..............................33 4...........................................19 3.......1 Filling the coulometric cell ..........................4 Generator electrode without diaphragm .....8 2.......38 5 Sampling ..........3..................................................24 4........................1......................21 3.....4 Concentration determination with pure water....................4..5 1......2 Two-component KF reagent .1 KF coulometry .. The Karl Fischer titration...............................13 3....28 4.............2........21 3..................................................................0 mg/g ............................19 3...2 The minimum and maximum dosing rate ...................................1 The influence of atmospheric humidity (drift determination) ...2..........................................2...........2..................3 Volumetric KF Titration: Titrant concentration..........................1 Titration stand ......................................................

.81 11...........................................................................2 Liquid samples ........................................inorganic .....................................45 7 Release of water from the sample .........................3 Reaction with iodine .......................................1 Effects of temperature...........................3 Technical products – organic .........................................49 7...70 9...............................................................................................................1........................................88 11................................1...................................................................................................................6...............................1 Coulometry......................................................................................................78 11..............1 Solids: Characteristics.................4 Example: reevaluation of side reactions ............................................................................................87 11.....................2 Coulometric methods .............................................................................................83 11...................................................................................................................................................6...........................4 Manual Karl Fischer drying oven..........................................4........................................................77 11....40 6 Sample addition .................................................................................2....................2........90 2 ..........43 6................................4 Liquids: Sample input............2................................................47 7....3..................70 9.....1..................................................5 Technical natural products ..................................................................................................4...........................71 9..........1.1 Taking the sample.....................................................................................2..............60 7.....1 Liquid samples ................6.........................................................................................................................................................75 11 Karl Fischer Titration: The Method at a Glance ................................57 7.........................................1 Organic and inorganic chemicals .3 Titration Methods ..................................................78 11..............................6............................................................80 11........................83 11.............................................................2 Foods and technical products ........................1 Solid samples.................1.................2 Reaction with water.................................................................................86 11....79 11..............................................55 7.................................................4...........................71 9.........3 Amount of sample ................................2 Purge gas...................................................6 Determination using the drying oven ...................1 Internal extraction .....1 Reaction with methanol......................73 10..................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5..........86 11............................................2 Storing the sample ...........1 Organic Chemicals..................................................................................62 8 Measurement results ..................5 Additional literature ............67 8............................................58 7................................................70 9...............................................................4 Sample preparation and input .............5 Determination of water in gases ...........89 12 Appendix .................................72 10 Troubleshooting ................77 11.......................................................................................................................................................87 11................................................................................................................68 9 Interferences .........................................................................67 8.3....................................................................................4 Lyophilized substance in septum bottles.....................39 5..............................80 11.................48 7...........59 7................43 6.1...........................................77 11...........................................87 11...3 External dissolution ..................2 Solids: Sample input ..........................................................3 Repeatability ......................1 Resolution and detection limit ..1 Principle ...............79 11...................................2 Inorganic chemicals ...............3 Procedure....................................85 11............3 Liquids: Characteristics ...........................................2 Solid samples.....................................................................................4 Technical products ......................2 Measurement accuracy........................4....................................................................67 8.............................79 11...........6....................2 Volumetric Karl Fischer Titration .............................................................................................1 Volumetric methods ...............................................................2 Side reactions ................................................39 5............................................................................................................................................................................................................................................................73 10...........................................58 7......................................6 References...........................................................................................4..............5 Accessories for sample input .............................................................58 7.....................4................................................................................................................71 9........................................................................2 External extraction ...........................................................................................5 STROMBOLI automatic oven sample changer .....................54 7........6 Food .............................................................86 11..............................................................................

...6.................................4.1 One-component reagent ....91 12........................................94 12..............92 12......95 12....................................................................................1 For samples soluble in methanol or ethanol ...METTLER TOLEDO Good Titration PracticeTM in KF Titration 12...........4..............6..............................98 13...................................2 For samples poorly soluble in methanol or ethanol...........................................96 12.........98 13...................................................................................97 13 Hazards and waste disposal tips ..............................4 For ketones and aldehydes...................5 For acids and bases (pH value) .....1 Formula for the external extraction ................98 3 .....................................95 12.98 13.........................91 12..............95 12...................................................1 For samples that are soluble in methanol or ethanol .....................93 12....................3 For samples insoluble in methanol or ethanol...96 12...........................6........3 Reagents for coulometry: ............................93 12........................................................................98 13..............5 For acids and bases (pH value) ...............2 Two-component reagent: .............4 Reagents and solvents for coulometric analysis ..6 Titrants and solvents for volumetric analysis ...............................................................2 Formula for the external dissolution ...........................................95 12...................................3 Standards for Karl Fischer coulometry............................4 For ketones and aldehydes....................................................................................................................6.......................................90 12...........4 Safety data for the KF-components and auxiliary solvents: ............4..92 12...........5 Water Standards for Karl Fischer volumetric titration.....2 For samples that are poorely soluble in methanol or ethanol ..4..................92 12..................................3 For samples that are insoluble in methanol or ethanol ..............................................................................6............................................4.....................................

First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). titrant specific standard parameters and LEARN titration. by G. First diaphragm-less cell for coulometric KF titration. M. Publication: Coulometric Karl Fischer Titration by A. Improved METTLER TOLEDO DO307 KF Manual Drying Oven.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. Jungnickel. Enormous spread of the use of KF titration. Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available. 2000 2001 2002 2008 4 . and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control.0. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. and solvent dispensing and removal. Meyer and C. D. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation. S.J. DL37 KF Coulometer from METTLER TOLEDO.Boyd [4].3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. Publication: “The Dead-Stop End Point“. 1. April 1956. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. promoted by publications by E. Solid KF Oven Standards with water contents of 5. Automatic KF titration instruments with piston motorized burettes. Wernimont and F. They replaced the DL18/35 KF Volumetric Titrators. 0. Use of Karl Fischer method spreads.Direct method”). Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm). Peters and J. Hopkinson [2]. Water standards (10. First German DIN standard for the Karl Fischer titration (DIN 51777. First coulometric KF titration instruments are commercially available.0. respectively. Publication on stabilized single-component Karl Fischer reagent by E.5% and 1%. L. Pyridine-free KF reagents are commercially available.1 mg/g) with test certificate according to DIN 50049-2. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. Eberius [3].METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. Introduction of less poisonous KF reagents based on ethanolic solution.

depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4). Bryanz and Mitchell [6] formulated a two-step reaction: 1. Karl Fischer used pyridine for this purpose.5.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. I2 + SO2 + 3 Py + H2O → 2. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction.5 to 8. the maximum reaction rate is reached here and cannot increase further. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1].METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. and the faster the rate of the Karl Fischer reaction. In an alcoholic solution. it only acts as a buffering agent and can therefore be replaced by other bases.. I2 + SO2 + 3 Py + H2O → 2. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. W. the more methyl sulfite is formed by the capture of protons. described by the rate constant k. At pH values above 8. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. The rate of the Karl Fischer reaction. i. all the sulfur dioxide is present as methyl sulfite.e. Methanol proved to be suitable as a solvent. but rather the methyl sulfite ion. In order to achieve an equilibrium shift to the right. methanol not only acts as a solvent but also participates directly in the reaction itself. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. C. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1. In an alcohol-free solution. the 5 . Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations. Smith. Verhoff and E. In the pH range 5.

methanol) (e.C. With acidic or basic samples. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. methoxyethanol. Studies by E. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction.g. ethylene glycol monomethyl ether. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. A. Methanol should therefore always be present in the minimum required amount.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5. ROH + SO2 + RN 2. you can use other alkohols such as. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. diethylene glycol monoethylether) [10. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. ethanol. however. is not a serious limitation because the water concentration in the solvent is usually much less.g. In 1988. This. pungent pyridine. for instance.g. and for bases: salicylic acid). for determination in ketones or aldehydes). E. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. pH values less than 4 and greater than 8 should be avoided in practice. Verhoff and E. in a titration. If a methanol-free titrant has to be used (e. This improves the titer stability. this results in a more sluggish endpoint and higher iodine consumption. On the basis of this knowledge. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8].5 to 8. This reagent not only replaced the toxic. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. J.g. 6 . and references therein]. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. 2-propanol.

1 One-component KF reagent The titrant contains iodine.. i. The reagent can be stored for approximately two years. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration. sulfur dioxide and imidazole. 7 . 2 mg/mL for samples with a water content of less than 1000 ppm. Suitable for samples where water is present in trace amounts: 1 ppm . The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%. Suitable for samples where water is present as a major component: 100 ppm .METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration.1 Volumetric KF reagents 2.5 mg/mL per year in a sealed bottle. is approximately 0. You can also use a methanolic solvent mixture specially adapted to the sample as the solvent. 1 mg/mL for samples with a water content of less than 200 ppm.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration.1.e. the decrease in concentration. dissolved in a suitable alcohol. The drop in titer. where a solution containing iodine is added using a motorized piston burette.5% 2. Coulometric Karl Fischer Analysis. The solvent is methanol.

2 mg/mL for samples with a water content of less than 1000 ppm.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. methanol. High titration speed. such as amines. or an alcoholic mixture. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. This special reagent is also suitable for substances that react with methanol. HYDRANAL® (Composite 5K and Working Medium K. imidazole. 2. The solvent contains sulfur dioxide. These solutions are mixed 1:1 just before use to form the one-component titrant. To improve stability. This reagent is declared as “rapid”. and results in higher titration speed. which allow for fast and accurate Karl Fischer titrations. The titration takes slightly longer than with the standard KF reagent.1. + Simple handling. 8 . e. dissolved in an alcohol (usually methanol). The solvent is either methanol or consists of methanol mixtures. whereas the solvent contains 2-chloroethanol and trichloromethane. Two-component reagent: The titrant contains iodine dissolved in an alcohol. One-component reagent: The titrant contains iodine. reagents containing pyridine are still used because they are cheaper and can be made in-house. Note that it may be necessary to adapt the end point value in the titration method to these reagents. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. stable titer. Both the components are very stable in storage. dissolved in methanol. Reagents One-component Two-component 2. The separation into titrant and solvent improves stability of the KF reagents. imidazole. provided that the bottle is tightly sealed. whereas the solvent consists of sulfur dioxide and a base.g. pyridine. additional water is produced and titrated at the same time. – Titer less stable. As a result. methanol). from Sigma-Aldrich) and e. Special methanol-free KF one-component reagents such as e. titration speed slower. A titration speed two or three times as high can be achieved with the two-component reagent. sulfur dioxide and 2-methoxyethanol.1. leading to higher water contents and a vanishing end point.g.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents.1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. Solvent capacity restricted. favorably priced. from VWR/MERCK) are commercially available to prevent this problem. increases their lifetime. methanol) and B (iodine. imidazole and methanol.g.g. One-component reagent: The titrant contains iodine. sulfur dioxide and pyridine. The titrant has a stable titer. e.2 Two-component KF reagent The titrant contains iodine and methanol.

The generator is close to the measuring electrode*.1. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I . 2. however. a double pin platinum electrode. whereas the solvent contains sulfur dioxide. two-component.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction.2 Coulometric KF analysis 2. Both parts are separated by a diaphragm. the anode compartment and the cathode compartment. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. 9 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. The titrant contains iodine and ethanol. The classical coulometric cell consists of two parts. imidazole.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol. diethanolamine and ethanol. ethanol-based reagents were launched in 1998. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry. or “inner burette”) incorporated into the glass titration cell.2.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell.

Depending on the application.e. In Karl Fischer reaction two iodide ions. 2 [RN]H+ + 2e. This is the main product formed. i. 1C=1A·1s On the other hand. used to generate iodine.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment.e. octanol. as chloroform. Cathode reaction At the cathode. Anode reaction At the anode. I-. To calculate it. Methanol or ethanol is used as solvent. This consists of sulfur dioxide. Subsequently. I2. Note that methyl sulfonic acid. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). This can cause the cathode to become black. releasing two electrons at the anode. To avoid this. the positive hydrogen ions are reduced to hydrogen. present in the anolyte compartment. it is known that to produce one mole of a chemical substance that requires one electron. C. imidazole and iodide salts. The value 96845 C/mol is known as the Faraday constant. the catholyte should be replaced once in two weeks.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. which subsequently reacts with water. An ammonium salt is added to the catholyte in order to promote hydrogen production. are oxidized to one molecule of iodine. is the quantity of charge that is transported by a current of 1 ampere in one second. other solvents such e. iodine is generated from iodide by electrochemical oxidation. i. it is necessary to first recall the definition of 1 Coulomb: one coulomb. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. or the same reagent as used in the anode compartment. The cathode compartment contains the catholyte. 2 I. C.→ I2 → H2O 10 . hexanol or ethylene glycol may be added.2. CH3SO3H. 96485 C of current are needed. 2. The catholyte is either a manufacturer-specific special reagent. The negative iodide ions release electrons at the anode and form iodine.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. iodine reacts with water.

2. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard. 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore. this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10.712 C electrical current.).e. For an electrochemically optimized Karl Fischer cell. coulometry is designated as absolute method. Since current and time can be accurately measured. hexanol. For this reason. 2 x 96485 C/mol is required for 1 mole of water.4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. the current conversion efficiency for iodine production is assumed to be 100%. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. less than 3–4 μS/cm). Nevertheless. no standardization of the coulometric KF reagents is necessary. the maximum possible current applied by the instrument is 100 mA. Since the molar mass of water is 18. etc. 200 and 100 mA. 300. the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform.015 g/mol. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA). At very low conductivities (i.3 Iodine generation Iodine is generated by means of current pulses of 400. In addition. As a consequence. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . With standard conductivity values.2. it is used as a reference method for the determination of water content. the coulometer operates with current pulses of 400 mA. 2.

The latter can thus react more efficiently with water. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i.METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment.g. etc. Thus.phenols (most) esters . and for very accurate determinations. the cell with diaphragm may yield more precise results.acetamides etheric oils and essences . Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface. for measurement of samples having a very low water content (e. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. other easily reducible substances such as unsaturated fatty acids. The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . However. This is a very good reducing agent. To avoid this concurring reaction. especially when easily reducible. Nevertheless. Nascent hydrogen is formed at the cathode.2..edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. may also be reduced at the cathode by the formation of water. R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. 12 . 2. especially for nitro compounds such as nitrobenzene. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. lower than 50 μg water/sample). this makes it almost impossible for iodine to reach the cathode and be reduced to iodide.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. the cathode is a small-size pin). In addition. This effect is further enhanced by the small dimensions of the cathode. a different geometry is used for the generating cell without diaphragm.chlorinated hydrocarbons alcohols .ethers ketones (with special reagent) . it is still possible for a very small amount of iodine to reach the cathode. the relative error due to this effect can be minimized by using a larger amount of sample.e. In practice.

When the voltage drops below a defined value.the stirring speed and mixing of the sample solution.the viscosity of the solution and its temperature. . the titration is terminated.the termination of the analysis. Ideally. . constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. • • • As soon as all the water has reacted with iodine.the control algorithm and its parameters. A small.1. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy. 3.the reaction rate of the Karl Fischer reaction . . The resulting titration speed depends on the following factors: . the water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry"). there will be free iodine in the titration solution. there is no free iodine in the titration/anolyte solution. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant. iodine should be added or generated as quickly as possible. A high voltage is necessary to maintain the specified polarization current at the electrode. • • As long as the added iodine reacts with the water.1 Indication 3. and the addition or production stopped exactly at the end point. 13 .the addition speed or generation rate of iodine . The control of the titration is only possible if the end point is indicated. and hence.

where they donate the electrons and form an iodine molecule. 3. Above all.e. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. free iodine is present in the titration/anolyte solution. this value depends on the polarization current.the polarization current. i. Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. The two negatively charged iodide ions are attracted by the positively charged platinum pin. which are present in excess in the titration solution.e. At the end of the titration: As soon as all the water in the sample has reacted with the iodine. I2. This drop in voltage is used to indicate the end of the titration. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction".(to a lesser extent) the type of electrode (i. respectively. The iodine is present only at low concentration.METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. It then acquires two electrons and turns into iodide ions (2 I–). If mixing is poor. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. A voltage of ca. Ipol . again. • • At the beginning and during the titration: As long as the iodine generated reacts with the water. geometry and dimensions of the metal parts) . Iodide ions. then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. This free iodine gives rise to "ionic conduction".2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. 14 . the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. there is no free iodine in the titration/anolyte solution.the solvent or anolyte used in the instrument.1. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). The end point value mainly depends on . . no iodine reaches the negatively charged platinum pin.

This makes it more difficult to stop the titration at the right moment. With use. As a consequence.e. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. a double ring or plates instead of rings. i. iodine excess should be as low as possible to get accurate results. Sensors with a large platinum surface. The current density can be compared to a water pipe where a specific water has to flow. i. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). with longer pins. pin length: 3 . Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. the polarization current should be set as low as possible. pin length: 3 to 4 mm. In general the larger the platinum surface the smaller the current density.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. Sensors with short platinum pins (< 3 mm).4 mm. The layer is formed during the first ten titrations. a lower polarization current gives a smaller and steeper potential jump at the end of the titration.g.e. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis. and increases the risk of over titration. a layer is formed on the surface of the platinum pin sensor. 15 . and subsequently it remains constant. on the other hand. and increases the sensor resistance. exhibit a smaller potential jump. exhibit a larger potential jump and also a higher end point. On the other hand. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor. However. The larger the diameter of the pipe. e. With used sensors. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). just after the equivalence point. its surface can easily bond suitable chemical compounds. the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor.

3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. 2. the water concentration is lower. As a consequence.0 mL 1. sulfur dioxide is present in large excess in the anolyte. Mixing is influenced by the 1. which gives a high reaction rate. [H2O] . Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. 3. Towards the end of the titration. It is consumed with each additional measured sample leading to a decreasing dioxide concentration. the water content is high.0 mL In the coulometric KF analysis. [SO2] . Iodine generation or addition is usually the rate determining factor. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: . If the speed is too slow. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. point of titrant addition (volumetric KF titration). irregular. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent.the sulfur dioxide concentration. shape of the vessel (volumetric KF titration). In the volumetric KF titration. If 16 .2 min with a titrant consumption of 2. lower reaction rates are achieved with anolyte solutions that have been used for a long time.the water concentration. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. On the other hand.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition. At the beginning. the titration may also be too slow. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present.and on the iodine concentration. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant. and overtitration may occur. stirring speed. a large excess of sulfur dioxide is present in the solvent.5 . [I2] . with the twocomponent reagents.3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations.

the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. Furthermore. If a longer stirring bar is used. leading to slower addition and longer titration time. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. This is essential for a fast reaction rate and for short titration times. 17 . turbulence is not achieved and the mixing effectiveness is lower. Bubbles falsify the measured values. Otherwise the sensor may directly detect added iodine. the stirring speed is too fast. Iodine would not be distributed upwards.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. but rather along the base directly towards the sensor. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant.

4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents. The following drawing reveals a schematical illustration of the control band: 18 . The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3. The dynamic behaviour of the control can be influenced by a variation of the control band.1 The Control Band The control band is a modifiable control parameter for both types of KF reagents. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters.4. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3.

The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt. 2. Thus. at higher water contents. Recommendations 1. 3.. the end point must be adjusted. the titration starts with a slower acceleration (ramp up) than in the normal mode. however.4. Dosing rate (max) = 2 mL/min. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up.e. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. if the control band width is decreased. i. 3. In particular. In the cautious mode. The end point for a specific polarization current is influenced by the sensor and the solvent. In this case you can activate the Start: Cautious parameter. if the polarization current changes. The maximum dosing rate is dependent on the actual burette size. the control reacts more sensitively to potential changes. 19 . the titration starts so quickly that overtitration may occur.4 Polarization current and end point Each end point is valid for a specific polarization current. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. which leads to a stronger reduction of the dosing speed. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously. e. The closer the potential to the end point. sensors with very short platinum pins (< 3 mm). The following points represent possible contributing factors: contaminated or old sensors. 3. the titration will take too long. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. the titrator automatically issues a warning.4. This is more suited for small water amounts.4. With large amounts of water. the slower is the titrant addition.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control.3 The Cautious start If the water content is very low.g.

the system reacts slowly in the case of ethanol based reagents.g. the overall ionic conductivity is decreased. • If 1-comp titrants are used. 2-propanol. If one-component reagents are used. e. the titration can be accelarated by reduction of the control band to 300 mV.4.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. table) work fine. • • If 1-Comp titrants are used with Ethanol (e. used as solvent. • If 2-comp titrants are used.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. Ethanol-based reagents • Compared to the methanol-based reagents. Auxiliary reagents • If formamide is added to the solvent. this results in an illdefined titration end point. setting up of the titrant as 1-comp KF titrant yields shorter titration times. 20 . Composolver E) the standard 1-Comp parameters (cf. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. This results in a lower voltage required to maintain the polarization current. the overall ionic conductivity is increased. Therefore it is recommended to decrease the polarization current to about 15 μA. the sensor current shall be reduced to 15 μA. If 2-comp ethanolic reagents are used.g. • If Chloroform or Xylene is added in order to dissolve oil samples. 3. the titration curve is more or less flat towards the end. instead of methanol or ethanol. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. This measure allows the system to cope with the reduced conductivity. up to 8 mL/min for most 2-Comp 2 titrants. which will lead to long titration times and to low precision. In order to achieve a good repeatability.

which is the case in 1-Comp systems.6 General recommendations 1. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. Cautious Generator current: Automatic. If the titration takes too long. Fix (400. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate. the 1-Comp control is suitable for systems that show an oscillating potential behaviour. Furthermore it is recommended to reduce the polarization current to a value of 15 μA. 2. an increase of the control band is recommended. where the methanol has been replaced by e. In most cases 300 – 400 mV are well-suited. There is no need to accurately adjust the control band to the actual start potential.4. In general. 3.5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. 200.g. 3. 100 mA) 21 . E E t Oscillating system behaviour. which is the case in some ethanolic reagents. 2-methoxyethanol. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. 300. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. However the control band shall not exceed the start potential. The minimum dosing rate shall be used to fine tune the final phase of the titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones.

high resolution burettes (0.Fix). relative drift stop. The iodine generation starts slowly. 300. the iodine generation is higher than in the cautious mode. minimum titration time 22 . The closer the measured potential value from the predefined end point is. 3. In addition. pulse frequency and pulse height (mA) are used as variables by the instruments. iodine is generated by means of current pulses of 400. absolute drift stop.25 µL for a 5 mL burette).e. More specifically. Later on.e. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new. the slope of the iodine generation rate is flat at the beginning of the titration. as soon as the was potential value was lower than the set end point during the defined delay time. i. Normal: This iodine generation mode is generally used for all water content determinations. Cautious: Suitable for samples of low water content (e. and improved KF titration stands (i. less than 50-100 μg water per sample). Variation of pulse length (time). the slope of the iodine generation is steeper and the rate is increased based on the measured potential value.g. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity.e. i. maximum titration time. Five termination parameters can be defined in the titration method: delay time. Since the first developed KF reagents reacted slowly.e.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. a delayed switch-off time of 10 to 20 seconds was set at the end point. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. 2. then the titration was stopped. or it can be set to a specific value (“Generator current” . the slower is the generation of iodine. Initially. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. pyridine-free reagents with a faster reaction rate. In particular. i. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”.. 200 and 100 mA. This parameter shortens the titration time and leads to repeatable results. tightly sealed stand).METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter.

Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. 15 s) following the addition or generation of iodine. especially if working with the KF sample oven. 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. 23 . 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration. titrant concentration (volumetric) and side reactions. the titration is terminated and the result is printed. Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value. The smallest increment must be sufficiently large to compensate the drift. Disadvantage: The value optimized to the initial drift. • Advantage: This parameter ensures a high repeatability of the results. has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. the absolute drift stop value must be greater than the initial drift. Typical absolute drift stop value: 3 µg/min (coulometric). After the defined time has elapsed. Typical delay time: 5 .g. . easy to understand (volumetric).15 seconds (Coulometric/Volumetric) • • Advantage: well-known method.e. Thus. Typical value for the relative drift stop = 2-5 μg/min (coulometric).METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e. otherwise the termination criterion is never satisfied.Maximum titration time The titration is terminated after the defined time.m the drift before titration) and the relative drift. otherwise the termination criterion will never be reached.

Maximum titration time for determinations with the KF drying oven When using the drying oven. you can ignore these traces. but involves a risk that the titration will be terminated a bit too early. The vaporization of water is also irregular in the final stages.. Thus. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes. so 24 . possibly resulting in poorer repeatability and lower water contents. Use the drift/time curve to determine this value. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min). volumetric). A relative drift stop of 20 to 30 µg/min shortens the titration time. This parameter is independent of the the initial drift (coulometric. The final traces are only extracted very slowly. this is the simplest and most universal parameter to use.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). soluble samples You should normally choose the relative drift stop as a termination parameter. and the titrant concentration (volumetric). The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular. the drift at the end is often greater than the initial drift.6. If the water content is relatively high. i.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free.METTLER TOLEDO Good Titration PracticeTM in KF Titration . This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration. A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. It is recommended to be used for substances that release water slowly.e. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. 3. • Advantage: This parameter ensures a high repeatability of the results.

METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. you should take measures to reduce the drift. Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. A combination of the relative drift stop and the maximum titration time has proved effective for such samples. (Set the minimum titration time equal maximum titration time). Therefore. If the drift stop value is not reached. If the drift is greater than 10 µg/min. It gives you the best accuracy and repeatability of results. The higher drift is therefore influenced to a large extent by the sample. This is the case with samples that only release the final traces of water very slowly or that produce side reactions. 25 . the titration is terminated at the latest after the defined maximum time. Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. the maximum titration time has proven to be best termination criterion in practice.

where the relative humidity can achieve values of more than 80%.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent). The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. the residual moisture dissolves more rapidly into the anolyte (solvent).1. 26 . it is titrated to dryness during pretitration. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. After the anolyte (coulometer) or the solvent (volumeter) has been added.4 weeks (indicated by a colour change of the indicator of the silica gel). Silica gel can be regenerated over night at 150 °C. i. however.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. until it is absolutely free of water. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel).METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. The drift. Briefly. since cold air cannot absorb as much moisture. However. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. In this way. When you assemble the titration stand for the first time. there will be moisture on the glass surface of the titration cell and the inserts. Moisture can enter the sample. The following rules should be observed: • • Close all openings in the titration stand.e. The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . Do not shake too vigorously to avoid solvent gets on the cover of the vessel.3 hours. the relative humidity increases. The air within the titration vessel also contains moisture. the titrant and the titration stand. This problem is particularly relevant in tropical climates or in coastal regions. whereas molecular sieves require temperatures up to 300 °C. The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture. This can take 1 . the greater is its influence on the results of the Karl Fischer titration. The air-conditioning system should therefore be equipped with a moisture condenser. the higher the atmospheric humidity in the laboratory. Condition the titration cell before use. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls.

it is necessary to quantify the amount of water entering the titration cell during titration. In this respect.1. t. the KF titrator continuously titrates the water that diffuses into the cell. traces of water will always find a way into the titration cell. On the other hand. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”.2 The drift No titration stand is completely water tight. At the start of a sample titration. In the standby titration. the drift value should therefore be as low as possible and stable before the start of a titration! 27 . Therefore it must be taken into account when calculating the water content. this water amount is also titrated during analysis. or a fixed value can be defined into the titration method (“Fix value”).METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. and its value is displayed on the screen.(drift * titration time). it is also possible to use the value of a previously performed drift determination (“Determination”). or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . On the other hand. Therefore. For accurate results. and is given in μg water/minute. the last measured drift value is automatically stored. the drift indicates the quantity of water that enters the titration stand over a defined period. This is achieved by titration of the dry solvent for a defined time (drift determination).

. . when the drying oven is used. . In this case. some anolyte solutions contain an excess of iodide and the solution has a brown colour. a flow occurs from the cathode compartment to the anode compartment.Make sure that the level of the anolyte is approx. 2.5 mm higher than that of the catholyte.Pour approx.Then fill the anode compartment with approx.Take approx. .The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation. you must add some methanol or sample so that the color changes to yellow. the level of the anolyte increases. Higher anolyte level → low drift Lower anolyte level → drift is high . By ensuring that the level of the anolyte is higher than the one of the catholyte.When a sample is injected into the anode compartment. The catholyte always contains traces of water. which leads to a higher drift. If the level of the catholyte is the same or higher.1 Filling the coulometric cell • Cell with generator electrode with diaphragm . the levels slowly become the same. This can be avoided as it follows: 1. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. the level of the anolyte drops due to evaporation. As soon as the stirrer is switched off.5 cm into the electrolyte solution. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed.The generator electrode should dip approx. the moisture enters the diaphragm and is slowly released into the anode compartment. Note: In production. The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant. 100 mL electrolyte solution (anolyte) into the titration cell. 28 .2. If this is not the case. • Titration cell with diaphragmless generator electrode .2 Working with the coulometric KF instruments 4. . 3 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. 100 mL anolyte. 2. However.First transfer 5 mL catholyte to the cathode compartment. the anolyte should be topped up from time to time with anhydrous methanol.

2. Any contact with the reagent is avoided during draining and refilling of the titration cell.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. and the risk of over titration increases. A level sensor in the waste bottle prevents from overflow. It is fully controlled by the titrator.Anolyte solutions (100 mL): after 1000 mg water. With poorly soluble samples. The capacity is monitored by the coulometers (see operating instructions). If the drift is too high. In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift.Catholyte solutions (5 mL): after 200 mg water. • • • • • 4. If the conductivity of the anolyte drops to a very low value. In practice.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. the worse the stirring efficiency will be. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 . If an electrolyte is used for a long period without replacement.3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. The higher the level in the anode compartment. . If an emulsion forms in the anode compartment.2. the level of the solvent or the anolyte exceeds the 150 mL mark. This can happen if large amounts of samples of low conductivity are titrated. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. e. when using a generator electrode with diaphragm. This can lead to wrong results. After being used for two weeks. below 10 μS.g. . the drift slowly increases.

Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen. Step 2: The Anolyte is drained into the waste bottle by applying vacuum.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. 30 .

The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. In this configuration only draining of the titration cell is possible. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air. An optional reagent exchange set consisting of tubes. drying tube and tube holder enables both draining and refilling.

The C30 provides a reagent monitoring routine which is called Reagent Control. The procedure is identical to that described above. The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated. • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. Simple cleaning and drying of the generator electrode Method A: .Methanol flows through the diaphragm into the cathode compartment. which leads to a higher drift. Method B: .Fill the generator electrode with anhydrous methanol. especially if dirty samples are analyzed. Methanol flows through the diaphragm and rinses out moisture and contaminants.Place the empty generator electrode in anhydrous methanol. . Afterwards thoroughly rinse the generator electrode with water. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier.Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. Moisture and contaminants are rinsed out of the diaphragm. . . the most effective cleaning agent is chromic acid. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due. Drying is not necessary if you use it immediately.This procedure should be repeated at least once. since it would cause a higher drift value. If immediate use is required rinsing with anhydrous methanol shall be applied.2. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. then with anhydrous methanol and dry it as described above. • 32 .

which prevents a good indication. We recommend to determine the titrant concentration daily.1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant. 3. the indicating electrode does not need cleaning.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days). The volumetric KF titrators enable monitoring of the usable life and life span of the titrant.if the desiccant on the titrant bottle is "used up". The layer should therefore not be removed by cleaning. repeatable results.2. In this case. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. e. However.01 mg/mL per week. the one-component titrant. samples may be deposited on the surface of the electrode. a layer is formed on the platinum surface after the first few titrations. it is better to determine the concentration every 2 to 4 hours. • Clean the platinum pin with a paper tissue. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. The Ohmic resistance of the electrode is increased. The titrant is not chemically stable. This leads to a higher potential jump. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) . A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. 4. In the global settings within the setup menu of 33 . Based on the chemical stability of the titrant. 2. place the electrode in 0. the tightness of the titrant bottle and the desired level of accuracy.g. the measuring electrode must be cleaned. This test of the complete system by a titer determination is therefore an essential condition for accurate. 4. This also becomes noticeable through a dark coloration of the anolyte at the end point. .3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. while the two-component titrant is rather stable). In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. As already described.if the titrant bottle is not tightly sealed.5 Cleaning the measuring electrode Generally. 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped. 2) Connect the S7 connection of the generator cell with the indication electrode. This is sufficient in most cases. Their volume increases considerably with temperature.5 mol/L sulfuric acid.3. so that there is a sharp drop in concentration. • With heavily contaminated electrodes.

it contains 15. Either the user is simply warned or the usage of the expired titrant is blocked. Determine the concentration under the same conditions as for sample analysis. 2.e.08 g di-sodium tartrate dihydrate with the aid of a weighing boat. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate. Add it into the titration vessel.08 g/mol). Note: 1.using the same titration stand with the same volume of solvent. Since it slowly dissolves in methanol. i.3. The plastic tubing is not absolutely water vapor-tight.5 mL with a 5 mL burette. Determine the weight by back weighing and enter it as sample size.Use the optimized METTLER TOLEDO method M301 Weigh between 0. 4. Na2C4H4O6•2H2O (M = 230.and at the same temperature. Mix for 3 minutes to achieve complete dissolution before you start the titration.04 and 0. Rinse the burette 2 times into a waste bottle before you determine the concentration. Under normal conditions. This sample size yields an optimum titrant consumption of 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded.66% of water. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . i. - 34 .e. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time. 26-50 % of burette volume. . which prevents the execution of further titrations.3 to 2. Make sure that nothing adheres to the beaker wall or to the electrode.: .

05 g di-sodium tartrate). You must perform the determination in pure methanol! Highly soluble. This content is confirmed by the test certificate enclosed with every package. You can perform six determinations in 30 mL of Solvent* before you need to change it. Highly soluble. you should weigh in 1. mixing time 5 minutes. Thus. mixing time 1 minute.0 to 1. You must either change the solvent after every sample or use pure Solvent* for the determination.0" from Sigma-Aldrich® with 10 mg water in 10 g standard. Partially soluble. Less soluble. Partially soluble. Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL. "HYDRANAL®-Water Standard 10. mixing time 1 minute. The water standards are supplied in glass ampoules. They are thus protected against the ingress of moisture and can be stored for up to five years. You cannot perform more than three determinations in 40 mL of methanol (with 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results. mixing time 1 minute. too high titer). mixing time 2 to 3 minutes.05 g di-sodium tartrate dihydrate).5 g of water standard 10. You cannot perform more than one determinations in 40 mL of ethanol (with 0. You can only perform one determination in 50 mL of 1:1 mixture (with 0. A cloudy solution will falsify the results (i.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water. You must perform the determination in pure methanol! Less soluble.0. 35 . always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble. The values that are obtained are approx.g.3.3 Concentration determination with Water Standard 10. e. 30% too high. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4.e. Slightly soluble.045 g di-sodium tartrate). mixing time 2 to 3 minutes. The values obtained are approximately 10% too high.

5. Plastic syringes may introduce a small amount of moisture. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions. 4. the whole content of the ampoule is completely drawn into the syringe.4 Concentration determination with pure water General When using pure water to determine the concentration. Start the titration without any mixing time. Inject exactly 10. – – – 36 . The error is minimized by rinsing and conditioning the syringe beforehand. a very good deal of practice and precise working is required to obtain repeatable.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. 2. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e.0 µL deionized water with a 10 µL syringe.01 g as the sample size. In an open ampoule the liquid standard is exposed to air moisture. 6. Use a new ampoule for each new concentration determination. accurate results. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL.3. it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. Enter 0.g.01 mg (e. You can use a water standard with 1. Thus. with a Hamilton microliter syringe). A balance with a resolution of 0. To reduce the influence of the atmospheric moisture. The content of an ampoule is sufficient for 3 to 5 determinations. Open the ampoule shortly before the measurement in accordance with the enclosed instructions.g.5 mL at a time as an aliquot. Draw the whole content of the ampoule into the 10 mL syringe. the water content is increased and thus this will falsify the results.0 mg/g water standard.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. 3. Start the titration without any mixing time. The sample should be weighed either using a balance with a resolution of 0. Rinse a 10 mL syringe with approximately 1 mL of water standard. Inject 1 to 1. or with a 10. Determine the weight by back weighing.1 mg does not satisfy the requirements for a repeatable titration. Glass syringes are better. 4.

creams. kerosene Pharmaceutical products: ointments. if it is absorbent. Solvent Methanol Max. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. You can get rid of any bubbles in the syringe by expelling the water rapidly. - 4. All the screws in the syringe must be tightened securely. diesel oil. However. to avoid touching the glass part. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . tar products. caramel. Hold the syringe at right angles directly in front of your eyes to read off the value. lay it down on the adapter and empty it completely. the sample must release water completely. hydraulic oil. massage oil.5 The solvent To determine the water content in a sample. it may draw water out of the needle!). Always use a syringe with a long metal shaft. Insert the syringe through the 1 mm hole of the three-hole adapter. You can use mixture of solvents to achieve complete dissolution. yogurt. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. beverages Cosmetics: soaps. Only freely available water undergoes reaction with the Karl Fischer reagent. fat Oils: edible oil.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. suppositories Sugar products: jelly. fatty creams Waxes. After setting the volume. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. Always add each sample in exactly the same way. jelly bears Starch products: flour. 2. ethereal oils Petrochemical products: gasoline.3. ester Organic products: urea. corn. Adjust the plunger to exactly 10. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. amount 100% Samples Solvents: toluene. alcohols.0 µL. dioxane. noodles. Do not warm the syringe. transformer oil. salicylic acid Foods: honey. emulsions Petrochemical products: crude oil.

or the titration will take too long and titrant will be wasted. Therefore. i. or by indicating the maximum number of samples to be titrated. The amount of formamide at 50 °C should not exceed 30%.imidazole is used for acidic samples. starch products will not dissolve in it. The extraction capacity can be improved by increasing the temperature (e. too low water content. 4. If acidic or basic samples are titrated.3.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: . which may be completely expended if you titrate a large number of samples with high water content. the titration of subsequent samples will then be very slow. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong.e. the water will no longer be completely released.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. On the other hand. If exhausted.g. 50°C). In this case.salicylic or benzoic acid for basic samples. Sugar is the only type of sample that dissolves in formamide. The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. This will lead to incorrect results. you must replace the solvent timely. it is necessary to replace the solvent timely. The solvent for the two-component reagent contains SO2. formamide effectively extracts water from starch products. 38 . 3. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life. the amount of water in mg which has been titrated. 2. The solvents that are used should contain as few water as possible (< 100 ppm). and . Once again.

It floats on the surface or sinks to the bottom. it must contain the same average amount of water as the material as a whole.the most common source of error. and thus air moisture can penetrate the plastic and absorbed by the sample. you should determine its water content as soon as possible. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. 3. you will no longer be able to determine its true water content. the absorption or release of moisture.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. 5. e. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol.e. This can happen when a sample cools and the water solubility is decreased. rinse the bottles two or three times with the sample beforehand. 2. the water is not uniformly dispersed. 39 . water may be separated from the sample if it is left to stand for a long time. i. The sample must be representative. With liquid samples. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. or at least minimize. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. Use sample bottles with small openings to minimize the ingress of moisture. the lower the amount of moisture. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. Use bottles with a septum stopper for liquids of very low water content. The sample should be taken quickly to exclude. such as butter. oils. If you have to store the sample. 5. the sample should be larger the more heterogeneous the distribution of the water. 4. In such cases. "An analysis cannot be better than the actual sample!" When sampling. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. which cannot be mixed as thoroughly as liquids. Heterogeneous water distribution in samples: In non-polar liquids.1 Taking the sample When taking samples for water determination.2 Storing the sample After you have taken the sample. With liquid samples that do not dissolve water such as oils.g. you must be extremely careful to exclude atmospheric moisture . In the case of non-polar solids. you should take into account the following points: 1.

1 mg water per sample. sample size Amount of water [ppm] [g] [mg] 1 10 0.0 5000 0. A titrant consumption of 0. and the required accuracy and precision. approx. In general.1 1. the optimum amount of water is in the range from 0.5 to 2 mg water per sample. Repeatable results can be obtained even with 0.05 mg water per sample with a titrant concentration of 1 mg/mL. This corresponds to 0.25 100 4 0. the accuracy increases with the amount of sample.05 mL is thus still acceptable when using a 5 mL burette. 10-50 μg water can be detected if the demand for repeatability is not too high. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration. the optimum amount of water is approximately 10 mg per sample.4 500 2 1. and the following minimum sample sizes should be used: Water content Min.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5.0 10000 = 1% 0. Under optimum measurement conditions.01 10 8 0. As a rule of thumb. This corresponds to 7. For coulometric analyses. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.5 to 17.0 For volumetric titrations. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 .0 1000 1 1.08 50 5 0. For optimum accuracy with determinations in the range from 1 ppm to 1% water.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL. it is recommended to use the minimum sample size given in the following table: Water content Min.1 to 0. because the absorption of atmospheric moisture during sampling or sample addition becomes less important. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume. If a high level of accuracy is required.3 Amount of sample The amount of sample used depends on • • the expected water content.2 1. the accuracy is improved if larger sample amounts are used.1 to 0. because the absorption of air moisture during sampling and sample addition becomes less important.

1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content. The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF.METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. Logarithmic scale! 41 .

42 . an optimum sample weight range is recommended.METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. which is accessible in the online titrations screen: Dependent on the expected water content.

Fill the 5 or 10 mL syringe with sample after removal of the piston. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. 50 °C and fill it into a syringe. especially with samples of low water content. aqueous emulsions. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. In the case of a volumetric Karl Fischer titrator. toluene. Low water content Low water content Hygroscopic Viscous Very viscous ointments. suppositories b c Liquefy the sample in an oven at approx. Inject it into the cell using a wide-bore needle. In the case of a volumetric Karl Fischer titrator. Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. alcoholic beverages methanol. hydraulic oils. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. paraffin. yoghurt. edible oils hexane. you must take suitable precautions to prevent atmospheric moisture from being absorbed. honey a Waxy candle wax. creams. Possibly warm the sample slightly to lower the viscosity. silicone oil. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. ski wax. The syringe is heated together with the wax. 43 . benzene glycerol. This prevents the sample from solidifying in the syringe during the weighing.1 Liquid samples When adding liquid samples.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Enter the sample size in the titrator or transfer it automatically. If the sample is hygroscopic or has a low water content (< 1000 ppm). Replace the syringe with the remaining sample on the balance and back weigh it. Fill the syringe with sample and wipe the needle with a paper tissue. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. you must aerate the bottle with dry air (equalize the pressure). Air flows through the molecular sieve into the bottle when you take a sample aliquot. use bottles with a septum stopper and pressure equalization. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. Otherwise when the syringe is removed. Fill a syringe without a plunger with molecular sieves. To avoid this. Start the titration. a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. the drop will adhere to the septum. Empty the syringe (into the waste bottle) and repeat the rinsing two or three times. Withdraw the plunger and rinse the syringe with the sample by shaking it. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. seal it with cotton wool and insert it into the septum bottle using a short needle. – – – – – – – – – – 44 .

almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode. this would lead to an error of 5% to 10%. cooled analytical mill. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. about 50-100 μg water enter the anode compartment. pulverize less hard samples in a mortar.g. jellied fruits. cellulose powder: – Either weigh the sample in a dry box or extract it externally. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. For instance. it should be added under the same conditions as it was transported and stored. chocolate. depending on the ambient humidity. salts. For this reason. If possible. With an optimum sample size of 1 mg water/sample. 45 . The sample should be quickly weighed and added to minimize air exposure. coarse-grained samples in a closed.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. Hard. e.g. the storage of samples in a refrigerator may cause water to condense. Sample characteristic Brittle Hard/soft Pourable Procedure e.when the titration cell is opened to add the sample.g. – Add the sample with a weighing boat.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry . thus. salicylic acid. crystalline samples: Weighing boat – Grind hard. jelly bears. fatty e. e. solid fat: – Grate the product and add the sample with a spatula. in a volumetric KF titrator solids can be directly transferred into the titration vessel.g.

suppositories: – Liquefy the samples in a drying oven at approx. The syringe is heated up together with the wax. - 46 . to prevent the sample from adhering to the vessel wall or to the electrode. Add the sample into the titration vessel. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft. Do not use a syringe. Tare the balance to zero. – Add the sample with a spatula. Use a weighing boat with attached flexible tubing if necessary.g. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. Back-weigh the empty weighing boat. The water content is often lower atthe surface than inside the sample. margarine. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. chocolate cream. inhomogeneous e. candles.g. Start the titration. paraffin. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand.g. honey. because the water is released if it is pressurized Waxy e. butter. 50 °C and fill them into a syringe. Enter the weight in the titrator or transfer it automatically. ski wax. fatty.

g. water adsorbed on surface capillary bounded water (e. hard salts: Grind in a closed. e. meat. in plants) Water Example: Sugar. fatty Soft. it is necessary to crush insoluble solids in order to gain access to the trapped water. jellied fruits. This is not the case with solids if the water is bound as. The following methods are available: Sample characteristic Very hard Procedure e.g. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus.g. inorganic salts.: • • • • entrapped water water of crystallization (salts). Fibrous natural products Suspensions 47 . minerals. cheese: Hard. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. fruit juice extracts. noodles. sausage. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples. e.g. e.g. cooled analytical mill. grain.g.g.g. brittle Moderately hard. berries: Reduce with a homogenizer in an external solvent. brittle Viscous Hard. coffee beans: Crush in a mixer.g.g. e. organic salts. solid fat: Grate the product. then reduce it further with a homogenizer in an external solvent. fatty Mince the product. e. e. chocolate.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. e. vegetable juices: Reduce with a homogenizer. Sample preparation Water: Example: Biological samples First of all. dried fruit and vegetables. crystalline products: Pulverize in a mortar. e.

etc. grinding the sample additionally with a built-in homogenizer (see photos below).METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. potato chips.4 1.1 mg/pc 3.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel.8 1. hazelnuts.0 7.8 4.3 1.1 1.5 1. e.4 0. Water is then extracted providing the mixing time defined in the titration method is sufficiently long.1 4.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 .4 1.0 1. using either methanol or a mixture of it as the solvent. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.3 2.9 0.5 8.2 1.9 0. You can speed up the extraction of water from the sample by • • In many cases. the homogenizer eliminates the need to use auxiliary reagents such as formamide with. heating the solution with a thermostating titration beaker.g.9 srel / % 0. sugar.8 1.

sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. Pay attention to the water capacity of chloroform (max. edible fat) for natural substances (almonds. 350 ppm) and toluene (max.2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. In particular. 600 ppm). butter milk. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. pepper. 49 . water is extracted from the sample by means of a defined quantity of solvent of known water content. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. curry) for dehydrated products for sugar (total water). The extraction of water can be improved • • • by shaking the solution (mechanical shaker. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. Briefly.

- 50 .20 is normally used. Shaking is the method generally used for extraction. Step 3: Extraction - Shake. the smaller the relative error because the total error is calculated with respect to the sample size. or use a homogenizer. Add a sufficient amount of sample. A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight).METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. For the extraction of tablets. or use an ultrasonic bath with heating. the addition of dry quartz sand has proven useful for improving and speeding up the extraction. The larger the sample. A dilution factor of 10 .

take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm). Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix. 51 . % or ppm). Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . R: C: B: msol: mext: m: Note: Blank value (water content of the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling.

The weight of the solvent (msol).8 54. The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.3 0.4 4.6 61.5 9.4 0.3 0. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .6 72. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27.4 0.4 0.9 11.6 0.5 0.

METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible.e. Chloroform. In particular. 2. by selecting the appropriate calculation (i. 3. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. for instance. reaches the saturation limit for water already at 350 ppm! 53 . The amount of sample should also take account of the absorption capacity of the solvent. Note: 1. “External extraction”) in the method function “Calculation”. the formula is automatically given. The water content of the solvent should be as low as possible.

8 2.9 5. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 . External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results. %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. the addition of methanol is not necessary.2 10.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent.2 1. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent. waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4. or with a very low water content. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent). or with a high water content Pure solvents can be used to dissolve the samples. in % or ppm.

this error is reduced. 4. Draw an aliquot into the same syringe again. KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. Thus. 2. because a large sample amount leads to a too long titration time. 5. Determine the weight by back weighing. On the other hand. Since you are able to work with larger amounts of sample when working with this technique.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. Rinse the syringe two or three times in this way.g. Draw 10 . Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. Remove approx. 3. and too much titrant is consumed. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. Determine the weight of anolyte injected by back weighing. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. In fact. 6. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell.20 mL of anolyte titrated to dryness into the syringe. If the solid has a low water content (<200 ppm). the error obtained by direct titration if the titration stand is opened to add the sample is too large. 7. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. biological tissue. serum. the blank value correction is too large compared to the amount of water in the sample. 7. weigh it and inject it into the titration cell.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance. Direct titration is not suitable. the error as a result of opening the titration stand will be between 10 and 30 µg. 55 . weigh it and inject it into the septum bottle.

Alternative procedure: 1. 6.METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. 56 . 5. then you can additionally calculate the result can be given in ppm. zero must be entered for the blank value (B). Remove approx. With a standard method calculation and calculate the water amount in µg. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. 8. Rinse the syringe two or three times in this way. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. The accuracy of a plastic syringe is enough. 2. The water amount in µg is determined. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. If you know the lyophilized sample amount in the septum bottle. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. the final result must be multiplied by 4 (factor f = 4). the water amount in the septum bottle is 4 times larger. Since ¼ of the total amount was injected. 3. 4. 7. Thus. In this way. because the anolyte titrated to dryness has a blank value of "0".

Turn the three-way valve.If possible. time" and a "Delay time" of e. hydrochloric acid. water-free absorption liquid in which CO2 itself does not dissolve.Purge the sample vessel and the tubings thoroughly beforehand with the gas. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time.Calculate the volume from the time and the gas flow rate. Notes . you must fill the gas either into special gas sample tubes or into small steel cylinders. The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction. to ensure that the titration is terminated after the maximum time. . the gas must be directed through the titration vessel for a defined period of time.With sample vessels the gas amount gas can be determined by differential weighing.5 Determination of water in gases To determine the water content of gases.Purge the system with the gas before you start the determination.When titrating large quantities of gas in the same solvent.Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min. . . Determination . Sampling/sample addition . . . to prevent the gas from flowing into the titration vessel.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.Select "Max. start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel. . . 600 s as termination parameters.g. The gas must be directed through a water-dissolving. you should titrate the gas sample directly from the source.g. 57 .As soon as the drift is stable again. . .Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e. .Stop the gas flow after 1 to 2 mL titrant has been consumed. depending on the water content of the gas. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations. The water content in ppm is calculated by entering the volume and the density.CO2 gas can not be titrated directly since iodine reacts with CO2. If not.

6.6.2 Purge gas Air contains oxygen. the purge gases must be first dried before entering the KF oven. you should use a two-stage pressure regulator so that the final pressure is in the range 0.1 - The recovery rate is clearly decreasing with increasing gas flow rate. Air should therefore only be used for non-oxidizable. Thus.1 bar (cf. the oven temperature should not exceed 160 °C. 7. cf.6.6. that release water very slowly.5). For Karl Fischer titration. for accurate results do not select a too high gas flow rate. and the amount of water is determined.6 Determination using the drying oven This method is suitable for solids and liquids that 1.9 166 99. The purge gases commonly used contain moisture. cause side reactions with the Karl Fischer reagent.g. which could react with the sample at higher temperatures. or 2.7 500 97. The water is transferred to the titration cell in a current of dry inert gas (purge gas). 11 mg/L nitrogen gas from a cylinder: 1. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results. chapter 7.: o o air with 50% humidity: approx. causing the water in the sample to vaporize. chapter 7. 7. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99. If you use nitrogen from a gas cylinder. 58 .5 . e. If you use air for organic samples.1 Principle The sample is heated in an oven.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.0 mg/L Therefore.4 – 8. inorganic samples.4) A gas stream of approx. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven.

100% Phosphorous pentoxide. 2.6. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell.50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. in contrast to other desiccants. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. Silica gel and molecular sieves have the advantage that they can be regenerated.e. deactivate the drift stop). i. At the end of the titration. In the case of KF coulometers.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. the titration starts and the released water is continuously titrated. Silica gel can be regenerated over night at 150 °C. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample. all the water is vaporized and transferred to the titration cell. Silica gel is appreciably better in this respect. deactivate the drift stop). whereas molecular sieves requires temperatures up to 300 °C. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum.e. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. Method 1: The water evolved is continuously titrated After a short mix time (20 . It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves. they are rapidly exhausted. In such cases you should use the maximum titration time as termination parameter (i. you should set the maximum titration time as the termination parameter (i. but their water absorption capacity is low. The relative drift stop or the maximum titration time can be used as the termination criterion. To ensure that the determination is repeatable.80 µg H2O/L 40 . The KF titration is then started. there are two types of anolyte solutions: 59 . the vaporization is often very irregular.e. 7. In order to avoid the latter you may also use the minimum time as termination parameter. With some samples the drift at the end of the titration is significantly higher than the initial drift. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration.60 s). especially methanol.

oven temperature 200 °C: approx. as well as a gas flow meter. oven temperature 200 °C: approx. The recovery therefore depends on the amount of methanol vaporized and the method used. Coulomat AG Oven): Anolyte loss at 150 . Due to the vaporization of the methanol. This is particularly important with low-weight samples (e. there is a small loss of water.2 1.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. i. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . time 60 .g. 7.2 99. you should replace the anolyte lost through vaporization with new anhydrous methanol. 3.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e.200 mL/min. time Max.e.g. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!). fibers) or with samples of low water content. The procedure for the determination of water content is described in the operating instructions. dedicated anolyte to be used with a KF Oven (e.2 4.9 2.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C.7 99. Examples: Sample Result / ppm No. and the better the recovery.4.6. the faster the water is titrated.5 mL/hour Anolyte containing ethylene glycol. time Max. time Max.9 9. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99. 1 mL/hour – From time to time. time Max.e. It has a large glass sample boat capable of holding up to 10 cm3 of sample. time Max. the recovery is not 100%. i.95 98. An air pump is available as an optional accessory.200 mL/min.1 Briefly: The less methanol is vaporized.8 6.5 . of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0.

5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. If the drift is constant. 61 9. do not select the parameter "Auto start".7%. and does not drop into the cathode compartment/ titration cell. replace the silica gel and molecular sieves of the gas drying unit. Set a gas flow rate of 150-200 mL/min. Open the stop cock. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. This can happen when the titration is started only after complete evaporation. purge the "cold zone".METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%.55% or VWR/VWR/MERCK water standard KF oven 1%. In such cases. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. Then. This leads to a too low result. Some samples have surface water that is lost as soon as the oven is purged with dry gas. Some samples require some time before water starts evaporating. 6. evaporated solvent does not condense in the drying tube. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. 5. If the water is titrated as soon as it begins to evaporate. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). 4. you should proceed as follows: 7. To check the performance of the titrator/drying oven system. start the titration so that the drift value is automatically entered. For instance. For the same reason. bent drying tube. the evaporated solvent lost in the gas stream has to be replaced. . If several determinations are performed in the same solvent. in volumetric KF titration the methanol loss is approx. 10. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. 3. and/or replace the anolyte of the KF coulometer. If the drift is higher than 15 μg H2O/min. the recovery increases to 99. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5. A large amount of evaporated water cannot be fully absorbed by the solvent. 2. 3. Close the stop cock and purge the "hot zone".

the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. are included in the titration method. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer. 62 . 1 During a sample series: 2 3 1.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90.6. including the oven temperature. The drying oven can be operated in the temperature range from 50 to 300°C. while a glass tube pierces the aluminum foil cover. The blue rubber cap seals the sample vial tightly against the oven. 2. After the analysis. The oven heats the sample to the set temperature. The sample vials are moved upward into the oven by a lift. Besides 14 places for glass sample vials. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value. STROMBOLI is completely controlled by the titrator: all the parameters for the determination.

g. This takes 10-20 minutes as can be seen in the following diagram: 63 . fibers) or with samples of low water content. The drift value is defined as the moisture entered into the titration cell by the purge gas. To determine the drift value accurately. This is particularly important with light samples (e. the moisture in the empty sample vial has first to be removed. The sample vials are sealed with self-sealing aluminum foil and a rubber cup.METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack.

If this is the case.e. For each series. This means that the stored drift value of the previous determination will be used. The first sample of the next loop is then transferred into the oven and the water determination begins. as well as the anolyte in a coulometric analysis. a blank determination can be performed between two sample loops. If the maximum titration time is used as termination criterion in the method -which is what we recommend. drift value x time). a blank value determination should be performed before each series of samples since the ambient conditions (humidity. the vial used no longer has the same properties as the "fresh" sample vials. you can enter the number of samples the series includes for each loop. The loops run through one after the other and the samples are processed sample for sample. It is therefore not necessary to perform a drift determination before each series. and thus the moisture adsorbed on the glass walls is not always the same. suboptimum conditions.e. Thus. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. different plastic samples have to be analyzed. If. whose optimum bake-out temperatures differ.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. The blank value should be determined before each series because the humidity can change. i. the moisture content is somewhat lower. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i. The optimum blank value is in the range of 70 . At the start of the method. Nevertheless. In the same way. the method contains a so-called sample loop. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. it is important to use a new sample vial for each blank value determination (i. moisture in the sample vial. To determine the blank value as accurately as possible. the drift value can change with time. The blank value can also vary as a function of temperature. the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. gas flow. they can be measured at different temperatures using the same method. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. The new blank value is automatically used for the blank correction. for example. Performing the drift and blank value determination In general.g.300 μg water. the moisture in the air present in the vial. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. you can check whether the drift is constant and the new drift value can be used for the next series. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396). the blank value determination also takes the actual drift into account. In this case. In this case. etc. > 15 μg H2O/min). 64 .e.the analysis times for the determination of the blank value and for each sample are the same. These method templates are based on a dedicated KF method type called ‘Stromboli’. one with the same properties as the sample vials into which the samples have been filled in).e.) are always slightly different. By performing a drift determination at the end of the series or between several series. With rapidly changing. Important: After a blank value determination. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. If the temperatures of successive loops are different.

This valve shall be used especially if inert gas sources are used.g. Use the same vials for a sample series as well as for the blank value determination. With STROMBOLI. since it provides a leak free inert gas stream during normal operation. motor oil) or completely vaporized (e. 5. evaporated solvent is not condensing in the drying tube. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. This has a large effect on the blank value and thus on the result. 2. 7. These are partially vaporized (e. Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven. and therefore it does not drop into the cathode compartment. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. 4.55% or VWR/VWR/MERCK water standard KF oven 1%. 8. drying and storage). 3. 6. In this way. see also list of results).g.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. A sudden shutdown of power immediately switches the valve in that way. toluene. bent drying tube. you can not only determine solids but also liquid samples. Set a gas flow of 40–60 mL/min. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. This test also serves to check the tightness of the oven and the connection tubing 65 . A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. To check the titrator/drying oven system. The delivery tube has a T-piece that causes a small leak flow.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

68

69 .25 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs.0 5.0 3.0 Sample size (g) In both cases. it is necessary to use the optimum sample size in order to achieve precise results. sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0.5 1. with decreasing sample size the relative standard deviation srel becomes worse. A good repeatability is achieved the sample size is increased particularly for low water content values. Therefore.0 2.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

70

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Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

71

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Good Titration PracticeTM in KF Titration

The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

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1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .Increase end point Oven: water vaporizes very slowly and irregularly .Use smaller sample Long titration time.Increase value for rel. 1 mg water per sample is present.Increase amount of sample to ensure that approx.Measurement electrode is faulty Titration stand not protected against moisture . Oven: . drift stop as termination parameter. . if possible increase amount of sample Wrong sample preparation and sample addition .Measurement electrode is not plugged in .Replace molecular sieves and silica gel in drying tube .Check whether titration stand is completely tight.g. Water distribution in the sample is not homogeneous .Clean the platinum pins of the measurement electrode with paper tissue .Replace anolyte .Homogenize sample.The repeatability is strongly dependent on suitable sample preparation and sample addition.Use rel.Use a different method Oven: water not completely vaporized .Use higher oven temperature . especially at low water content (< 1000 ppm) 73 .Use t(max) as termination parameter .Level of anolyte should be higher than that of the catholyte .Replace anolyte Amount of sample too small .Add a small amount of one-component KF titrant to the catholyte.Check whether titration stand is completely tight. titration never ends Very long pretitration Poor repeatability Wet anolyte .Increase vaporization time. . e.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10. increase t(max) Wrong control parameters . drift stop . .Higher oven temperature .Grease the tapered joints Moisture from cathode compartment and diaphragm .Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .Clean titration cell and generator electrode and dry at 50 – 80 °C .Lengthen vaporization time (increase t max) .

Add sample into KF reagents.Replace anolyte If this doesn’t help.Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: .Use fix generator current 100 mA . . 10 – 15 minutes .Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits.Too low value: see above “too low value” if this does not help. . bad repeatability With water standard 1. If the sample preparation and addition is not done carefully. bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 .1 mg/g .Lengthen vaporization time (increase t max) . the Coulometer must be adjusted With water Standard KF Oven 1 %.Use back weighing.Use smaller sample size Values too high The titration was too fast → overtitration .2 .Sample not thermal stable: Use lower oven temperature . Anolyte has too low conductifity .0.Use higher oven temperature .Replace or change the anolyte .Replace anolyte .Too high value: see above “too high value” . For samples with very low water content < 30 ppm .Reduce the value for rel.3 g Generator electrode is contaminated The black cover cannot be removed. It has no influence to the result. at 170 °C.Use start cautious Oven: . do not splash to the walls of the cell.Check drift and blank value . Sample not dissolved (emulsion) . Checking drying oven Out of limits. contamination with atmospheric moisture occurs. if it is defective. check generator electrode.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .use a bigger sample size up to 0.Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic.Extend tmin (minimum titration time) Incomplete sample addition .0 or 0. drift stop .Replace or repaire generator electrode.

Increase vaporization time. 75 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10. etc. drying oven.Use t(max) as termination parameter .The repeatability is strongly dependent on suitable sample preparation and sample addition. increase t(max) Long titration time.Grease the tapered joints Condition Titration stand . Side reaction of the sample with the KF reagent . Low water content (<1000 ppm)! . .Increase value for relative drift stop.Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture .Use higher oven temperature .Homogenize sample.2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration . .Use "Rel. e.Increase oven temperature .Extend tmax (maximum titration time) . . drift stop" as a termination parameter. titration never ends Wrong termination parameters .Use different method.Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water . Wrong control parameters .Extend vaporization time (increase t max) .see above Oven: .g.g.Replace molecular sieves and silica gel in drying tube .Increase endpoint potential Oven: water vaporizes very slowly and irregularly . if possible increase amount of sample. Titration stand not protected against moisture .Reduce sample size Poor repeatability of the results Amount of sample too small . e. Oven: water is not completely vaporized .Check and optimize control parameters.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker.Check whether titration stand is completely tight.Increase amount of sample to ensure 10 mg water per sample.Clean platinum pins of the electrode with a paper towel. Water distribution in the sample not homogeneous . external extraction.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .0 is a simpler and a more dependable method.Increase sample size up to 0.Change solvent.Reduce sample size Single values too high Control parameters too fast (= slight overtitration) .12 g in 40 mL. If the sample preparation and addition is done carefully.Sample is not thermally stable: Use lower oven temperature . Sample not dissolved .4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits.Extend tmin (minimum titration time) Incomplete sample addition .Extend vaporization time (increase t max) . Poor sample preparation and addition . Di-sodium tartrate has only limited solubility In methanol max. For samples with low water content < 400 ppm . bad repeatability 76 .Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted . drift stop .Change solvent or use fresh solvent after every sample. No more sulfur dioxide in the solvent .Replace solvent .Reduce dVmax and dVmax factor.Check drift and blank value .Use titrant with 2 or 1 mg/mL Oven: . 15 – 20 minutes . The concentration determination is correct only if the di-sodium tartrate has completely dissolved. Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results.Reduce the value for rel. 0.Samples of low water content (<1000 ppm) are always hygroscopic. With water Standard KF Oven 5. Determination of the concentration using di-sodium tartrate or Water Standard 10.Replace the solvent frequently. contamination with atmospheric moisture occurs.Use back weighing. Oven: . which dissolves the sample.Use higher oven temperature .Add chloroform or other solvent to methanol.55 % at 220 °C. .

bitumen V4. V3. V5 C20 V2.V4.V8 C20 V10. V3.V3. anthracene. C0 V2 C20 V15 Low pKa value: phenol. V3. toluidine Oxidizable with iodine: aminophenol Method V2.1. indole. nitrobenzaldehyde > C12 Stearyl alcohol. C24 Hydrocarbons > C12 Biphenyl.V3.V7 V2. o-cresol Side reaction: naphthol. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid.C22 V2. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0. salicylic acid High pKa value: 2-chlorophenol. diphenylmethanol Weakly basic pKa >8: Imidazole. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl.V3. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 . C0 V2.V4.V4. R-Br. C0 Peroxides V2. nitrotoluene.C22 V16 C0 V10 C0 Nitrocompounds V3.pyren e.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde. cresol. anisidine. V4 C20 V2.: benzamide.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. C20 V11 C0 V2. R-I R-NCO Benzophenone Method V2.V5 C20 Ethers Linear and cyclic V2. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11.1 Solid samples 11.V5 C20.V4.V3 C20 di-Nitrobenzene.V5 C20. e. oxalic acid Oxidizable with iodine: ascorbic acid V2. C0 Sulfur compounds Phenols V0. V4 C20 Mercaptans V0. naphthalene > C20 Tar. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine. V4 C20 V15 C20 V0. V4 V2.

paraffins: shoepolish. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . e.g. V8 Cosmetics Creams. NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . NaAsO2 KHCO3 . V5 V12 V2 V40. V5 V5 V2 V20 V2 V5 V30. creams Suppositories Tablets Lyophilized preparations V2 V4. glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. V31 C31. NH4NO3 Nitrites NaNO2 11. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2.1. V30 Insecticides.1. fungicides. V31 C32 V2. bitumen lubricating grease. etc. V32 C20. KJ. V32 C21.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. dispersion dyes Waxes. Na2HPO4 tert. C34 V31 C33 V2. ZnSO4 V2. H3BO3 NaOH. ski wax Tar. C34 V10 Na2HAsO3 . V31 C20. lotion Lipstick Soaps Toothpaste V4.: Na3PO4 Silicon oxide. PVC. C34 V2. herbicides Soluble: wool dyes. 78 . multipurpose grease V2 V2. V32 C20. C32 Pharmaceuticals Antibiotics. NaHCO3 Na2CO3 B2O3 . etc. Silicon dioxide Silanols R3Si(OH) Na2SO4. polystyrene. C34 V2. C32 V15. Phosphate. polyurethane. disinfectants Salves.C40 V2 Adhesives All-purpose glue. polypropylene. CaCl2 . V31 C20. V32 C21. Insoluble: pigments. HBO3 . oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. KOH MgO. CaO NaCl. V31 C20. indicator dyes. poly-amides.

(V30) Cheese. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. potato chips Potato flakes Dough.1. sea salt V23 V24. C30 V2 V20 Paper. (V25) V22. instant coffee. mixed spice Mustard Adherent moisture: plain salt. margerine. wheat. tea.4 Technical products . jellied fruits. perborates) without brightener Total water V30 V2 11. noodles. curry. V23 V30.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30. Zwieback Yogurt. candy.1. V23 Cacao. noodles. plaster. dried vegetables and fruits Hazelnuts. broth Biscuits. tobacco. sea salt Total water: plain salt. hardened fat V4. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 .5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30.. pudding powder. Zwieback. mayonnaise Shortening. caramel. ice cream Dried albumen Powdered milk V2 V13 V2. almond paste Instant ice tea. V23 Vegetable products V22.almonds instant coffee Fats Butter. corn. jelly Sugar: adherent moisture Chocolate Spices Pepper. rye. wood Cellulose powder Wool. silk 11. gummi bears. V21 Mortar.1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. jam Honey. coffee beans. meat spread. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13.

1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. cyclohexene. methylal C1 to C7 hexane. hexanol. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. hexylamine Reaction with methanol: aniline.2 Liquid samples 11. chlorobenzene. diamine Easily oxidized with iodine: hydrazine. chinoline Strongly basic: alihatic amines N-butylamine. ethylal. isobutane. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. dodecane > C14 heavy oil. paraffin Aldehyde Acetaldehyde. ethyl acetate Methyl chloride. dioxane. anisole Methyl benzoate. HNO3. benzene. pentane.2. nitrotoluene. disulfides sulfonic acids Mercaptans V1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. C1 Sulfurcompounds V1 C1 V0. t-butyl chloride. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. toluidine. crude oil. cyclohexane. acetic acid > C2 propionic acid. methylethylketone Ketones V10 C10 80 . HCl Nitrobenzene. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. chlorotoluene Acetone. acetophenone. petroleum. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. toluene. xylene C7 to C14 gasoline.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. transformer oil.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer. cream.3.2. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. wine. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk. 81 . refer to chapter 11. tinctures Cosmetics: perfume. liquor Pharmaceuticals: extrakts. massage oil Vegetable oils Technical oils Hydraulic oil. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. sunflower oil Pharmaceuticals and cosmetics: ethereal oils. brake fluid. sample input and titration methods.

In this case methanol is used as a solvent.1 Volumetric methods The methods have been developed using 2-component reagents. dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 .3.10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .3 Titration Methods 11.120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 .120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.120 s Delay time: 7 seconds.120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .10 minutes Direct titration methanol free Titrant: two comp. Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. These can be also performed using the one-component reagent.

20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate.150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 . 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .20 min With drying oven at 160 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat.20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 . Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 . Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe.

3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 . Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate.

tea. S11 S4. meat grinder. for very thick pastes drill hole in bottom of syringe. No further preparation necessary. margarine Phenols. cooled analysis mill. (Select stir time so that sample dissolves completely. ice cream. pepper. noodles. Use grate to reduce size.) S8 S9 S10 syringe with needle Ø 0. 1-decanol. In external extraction solvent (methanol. Inject into titration cell. wool. S5 S10 S8 Paraffins. creams gel. almonds. Stir.4 Sample preparation and input 11. tobacco. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. S10 S11 S10. paper. active ingredients Na-tartrate S9 S12 11. resinous Waxes Examples Butter. greasy Soft. Let solids settle and remove aliquot of remaining solution with syringe. potato flakes Tar.: CaCO3 . chocolate Method S1 S1. gummi bears. shake or sonicate. Press through small holes e. S8 S10 Property Soft. Use syringe with needle Ø 1. S3 S2. rocks e. silk Cheese. S11 S6. napthalene. At room temp. yogurt Salts. jelly.8 mm ) Fill in backend of syringe Procedure Grind in sealed. shoepolish Creams. coffee. cristalline products Wheat. formamide).8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. S10 S2.4. Pulverize with mixer. broth Hardened fat. honey.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. brittle Soft. bitumen Method S7. (Pre-heat syringe with hair dryer or in drying oven. Dissolve sample or extract water. 60° C. meat Jellied fruits. Pulverize with mortar.g. Cut in small pieces with scissors or knife. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard.4.g. formamide). After sample removal keep sample sealed. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. SiO2 Salts.5 mm or without needle. After sample removal keep sample sealed.1 Solids: Characteristics Property Very hard Hard. pastes Pulverized soluble Salves. S3 S10. or up to approx. Zwieback Dried vegetables and fruits. S10 S11 S4. almond paste. 1-decanol. Homogenize sample well. Melt sample.) Homogenize sample well. greasy Examples Minerals. S2 S1.

4.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11. salad oil Perfume. acetone. petroleum. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0.The pressure loss during sample removal must be compensated with dried air. acetic acid Silicon oil. glass Visco-Spoon™ 1 mL ME-71492 1.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. glycerine Hexane.Homogenize thoroughly by shaking or stirring prior to sample removal. 0°C in ice bath. toluene. Hygroscopic sample or low moisture content (< 1000 ppm) .3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic.15 °C . after-shave Beverages. detergents.Keep sample in a septum flask.8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. 11. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0. .8 mm) Injection with syringe (without or with needle Ø 1. aqueous emulsions Acrylic enamels. H2SO4. Boiling point 5 .Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes.15°C Examples Propanol. acetone. synthetic enamels. . glycerine Acetaldehyde Methanol. . milk.5 Accessories for sample input Syringe Injection needle Weighing boat.8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 . .8 mm) Inhomogeneous emulsions .2 mm ME-71483 ME-23951 ME-51107668 10 mL 0.Remove sample immediately.4. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 .5 mm) Injection with syringe after cooling sample (with needle Ø 0. gasoline.Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0.8 mm). .Cool sample to approx. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. .Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.4. crude oil. For each titration use 1 mL syringe (with needle Ø 0.

“Mechanism and reaction rate of the Karl Fischer titration reaction. S. 48. GRÜNKE.2412 (1939). “Reaktionsmechanismen in der Karl-Fischer-Lösung“.M. Anal. Chim. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. [3] [4] [5] [6] [7] 87 . Zweikomponenten Reagentien mit Imidazol“. Chem. Chem.C. 334. Fresenius Z.. Anal. E. SMITH. Analytical implications”. Electroanal. MEYER. Anal. 272 – 274 (1943). 2407 . Fres. 1999 (in German). D. 303.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. J. Anal. Electroanal. Chem. Potentiometric measurements”. 15 (4). 305-315 (1976). Thesis University of Hannover. BOYD. W. HOPFKINSON. K. J. Chem. SCHOLZ. 61. Rotating ring disk electrode meassurement .W. Diploma-Thesis at the University of Hannover / Germany. Anal.. 31 (2). J. Fresenius Z. SEUBERT A. 86. „Kinetics and stoichiometry in the Karl Fischer solution“. Soc. E.6 References [1] [2] FISCHER. BRYANT.. J. BARENDRECHT. Nature of the Reagent”.. J. Angew.. 1988 (in German). 306. Part I. Acta. Fresenius J. S. E. . 309.207 (1980). “Mechanism and reaction rate of the Karl Fischer titration reaction. E. 460-464 (1982). Part V. MITCHELL jr. [8] SCHOLZ... Chem. J.C.. Chem. 394 . SCHOLZ. Fresenius Z. “Karl-Fischer Reagentien ohne Pyridin“. 394 . 334. VERHOFF.C. Chem. Ed. 123-125 (1981). 139-147 (2000). F. See literature references in: EBERIUS. 407-415 (1978).. M. WÜNSCH. Z... WERNIMONT. Anal. 75.C. 30-32 (1981). SCHOLZ. Chem. 94. “Mechanism and reaction rate of the Karl Fischer titration reaction. [9] WÜNSCH. Ind.. Chem. Chem. 71.C. R. Amer. Electroanal. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“. 309. J. 256-260 (1989) (in German). P. Z. W. J. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”.S. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. WÜNSCH. Liebigs Ann. Chem. A. Chem. VERHOFF.4. “Analytical Procedures Employing Karl Fischer Reagent I.. Chem. Chem.... Neue Eichsubstanzen“. J. COFINO. VERHOFF. KOK. Anal. 16-21 (1989) (in German). „Karl-Fischer Reagentien ohne Pyridin. „Karl-Fischer Reagentien ohne Pyridin. M. VERHOFF.comparison with the aqueous system“. Fresenius Z. Chem. BARENDRECHT. 1. Fres. 75-80 (1978). 203 . „Wasserbestimmung mit Karl-Fischer-Lösung“. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”. [10] GRÜNKE. E. 705-717 (1976).. A. “Mechanism and reaction rate of the Karl Fischer titration reaction. 312. Anal. E. G.. 215 – 219 (1959). “Untersuchungen zur Karl-Fischer-Reaktion”. J. Anal. Chem 368.396 (1981). 395-403 (1977). 265 (1853). Electroanal.. BARENDRECHT. Verlag Chemie Weinheim (1954) / (in German). Part II. BUNSEN. Fresenius Z. E.396 (1935). G. Part III. W. C.. Rotating ring disk electrode meassurement“. Anal. „Karl-Fischer Reagentien ohne Pyridin. SCHOLZ. SEUBERT A. „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. 93. First and second order catalytic currents at a rotating disk electrode“... Both publications from: SEUBERT. Einkomponenten Reagentien“. Auflage.. Anal. Part IV.. J.. Chem. 86. E. E. VERHOFF.. G. „Mechanism and reaction rate of the Karl Fischer titration reaction. G.. PhD.J. Eng. Th.

D.. Diploma-Thesis at the University of Hannover / Germany. 1985. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications".METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. 1989 (German) 88 . G. Food Chemistry 96.. 1984.Theorie und Praxis“. „Untersuchungen einer Karl-Fischer-Reaktion“.. 2006.. „Karl Fischer Titration“. 11. 431-435 (2006).5 Additional literature HYDRANAL®-Manual.A. WIELAND. DE CARO C. SCHÖFFSKI.. DE AGOSTINI A.. K. RÜEGG K.. E. „Wasserbestimmung durch Karl-Fischer-Titration . M. SCHOLZ. Springer Verlag Berlin.30918 Seelze / Germany. „Eugen Scholz Reagents for Karl FischerTitration“. Sigma-Aldrich Laborchemikalien GmbH. GIT Verlag GmbH. Darmstadt / Germany.

WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent. % or ppm). WP: This is what we get from the calculation in the KF method. The sample P used for the extraction is not dissolved. For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%.1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm). 89 .

The sample P used for the external dissolution is completely dissolved into the solvent. 90 . Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. Blank value (water content in% or ppm) of the solvent.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial. the total volume is increased.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. Total water content (sample + solvent).3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0. Thus.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1.2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12. in % or ppm.01% VWR/VWR/MERCK APURA water standard 0.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0.

hydrocarbons (C10 to C20).4 Reagents and solvents for coulometric analysis To determine its total water content. etc. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12.4. more solvent can be added to the anolyte. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 .e. part of the water content is not measured. i.4. ointments. acetamide. 12.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. ethers. This means that if an emulsion is formed in the anolyte. In this case. nitrocompounds. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. A number of different anolytes are available to dissolve the various types of samples encountered in practice. Alternatively. the water content determined is lower than the actual water content of the sample. esters. chlorinated hydrocarbons (up to C10). edible oils. the anolyte must be immediately replaced. alcohols.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10). For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. the sample must completely dissolve in the anolyte. etc. This is limited to a maximum of 30% to prevent the conductivity from falling too low. If the sample does not completely dissolve. an emulsion is formed.

For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. If you measure ketones regularly.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water.4. Chloroform must be added to the anolyte to ensure the solubility of these samples. This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low. hydrocarbons (above C20).4. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. transformer oils. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. etc.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12. we recommend the use of a second titration cell. For cells without diaphragm: - Notes on ketones: - - 92 . the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences. silicone oils.

acetic acid.2 mL to 0. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. The larger the sample. The measurement should not be performed in the titration cell because the electrode introduces too much water. - - Notes on aldehydes: - - 12. 1 mL). This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). Measure the pH with a glass electrode adjusted with aqueous buffers. the more important the effect of side reactions becomes. In these cases the pH value of the anolyte should be measured. e.5 mL. however. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. Use the HYDRANAL® buffer (SIGMA-ALDRICH).g.2).5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. the drift is higher because of the very slow side reaction. the substances can. Choose relatively small samples (approx. benzaldehyde) can also be determined by coulometric KF titration. formic acid. take an aliquot of anolyte from the titration cell. It is important to note that alcohols that react with ketones should not be titrated in this reagent. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed. To do this.g. The use of imidazole increases the pH value in the anolyte. Basic samples must be neutralized with salicylic acid or benzoic acid. 80 mL of anolyte and 20 mL HYDRANAL® buffer. amines: - 93 .e.4. with reactive ketones such as cyclohexanone use only 0. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. Aromatic aldehydes (e. i. acetaldehyde) are oxidized at the anode with the formation of water. the pH value of the anolyte must be adjusted to the range 5.g. e. Fill the anode compartment with approx. Short chain aldehydes (e.: - For basic samples. With Karl Fischer titrations of acidic and basic samples. Coulometric KF titration cannot be used to determine these compounds. Fill the anode compartment with approx. etc. easily be measured with volumetric KF determination. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. The special reagent for ketones can also be used for other samples. After a longer standby period.5 to 7 (see Section 1.g. - For acidic samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples.

1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. esters. an emulsion is formed.6. chlorinated hydrocarbons (to C10). One-component reagents: 94 . the anolyte must be immediately replaced. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. This is limited to a maximum of 50%. more solvent can be added to the anolyte 12. 12. If it does not completely dissolve. i. ethers.55% (potassium citrate monohydrate). In this case. A number of different anolytes are available to dissolve the various types of samples encountered in practice. etc.6.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. edible oils. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12. In this case. acetamide. Alternatively.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10). The water content is declared on a test certificate supplied with every vial. alcohols.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. ointments.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. nitrocompounds.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0.2 For samples poorly soluble in methanol or ethanol These include: etherial oils.e. part of the water content is not measured. the result determined is lower than the actual water content. etc. hydrocarbons (C10 to C20).

Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. etc.3 For samples insoluble in methanol or ethanol These include: petroleum oils. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. Chloroform must be added to the anolyte to ensure the solubility of these samples. silicone oils. transformer oils. One-component reagents: 95 .METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM. or an acetal. with the formation of water.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. hydrocarbons (above C20).6. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low.6.

With Karl Fischer titrations of acidic and basic samples. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). amines: 96 . the more important the effect of side reactions becomes. the drift is higher because of the very slow side reaction. the substances can.5 mL.e. - Notes on aldehydes: - - 12. The measurement should not be performed in the titration cell because the electrode introduces too much water. If you measure ketones regularly. To do this. take an aliquot of anolyte from the titration cell. we recommend the use of a second titration cell. e. i. - For acidic samples. If you have titrated a number of ketone samples. however.g. Aromatic aldehydes (e. It is important to note that alcohols that react with ketones should not be titrated in this reagent. Use the HYDRANAL® buffer (SIGMA-ALDRICH). Coulometric KF titration cannot be used to determine these compounds.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents.g. with reactive ketones such as cyclohexanone use only 0. Measure the pH with a glass electrode adjusted with aqueous buffers. The special reagent for ketones can also be used for other samples.5 to 7 (see Section 1. easily be measured with volumetric KF determination. the pH value of the anolyte must be adjusted to the range 5.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift.2).2 mL to 0. benzaldehyde) can also be determined by coulometric KF titration. The use of imidazole leads to a high pH value in the anolyte. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. 80 mL of anolyte and 20 mL HYDRANAL® buffer. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes.g. formic acid.: - For basic samples. In these cases the pH value of the anolyte should be measured.g. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference. The larger the sample. Fill the anode compartment with approx. Choose relatively small samples (approx.6. etc. acetaldehyde) are oxidized at the anode with the formation of water. acetic acid. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. Short chain aldehydes (e. e. 1 mL).

90 mL of anolyte and 5 g salicylic acid or benzoic acid. iodine. 13. swallowed or allowed to contact skin. xylene or trichloroethaylene). Irritant when inhaled. Fill the anode compartment with approx. Keep container tightly closed. Safety: Highly flammable.: 11 °C MAK value: 200 ppm Highly flammable. chloroform.1 One-component reagent Composition: sulfur dioxide. swallowed or allowed to contact skin. Health hazard when inhaled. Health hazard when inhaled. Potential teratogen. swallowed or allowed to contact skin. Irritant when inhaled. Do not let reagent contact skin or eyes.1 ppm. 2methoxyethanol or diethyleneglycolmonomethylether). and solvent (methanol. buffer (imidazole) and solvent (methanol. Keep away from open flames or sparks.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: . Disposal: as an organic solvent. 13. Keep container tightly closed and far removed from open flames or sparks.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. Ignition temp. Health hazard upon inhalation. Health hazard when inhaled. 2methoxyethanol or diethyleneglycolmonomethylether). buffer (imidazole). Irritant when inhaled. poisonous when inhaled or swallowed.3 Reagents for coulometry: Composition: iodine.: 28 °C MAK value: 100 ppm Flammable. Disposal: as an organic solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. tetrachloromethane. 13. Keep container tightly closed. sulfur dioxide.: 87 °C Ignition temp. Ignition temp. Do not let reagent contact skin or eyes. 2-methoxyethanol). Disposal: as an organic solvent. The KF solvent contains: sulfur dioxide. Skin irritant. Safety: flammable to extremely flammable. oxidant Ignition temp. Keep away from open flames or sparks. Safety: flammable to extremely flammable. Ignition temp. 2-methoxyethanol.2 Two-component reagent: Composition: iodine and solvent (methanol. Do not let reagent contact skin or eyes.: 46 °C MAK value: 5 ppm Flammable. Poisonous when inhaled or swallowed. buffer (imidazole) and solvent (methanol. 13 Hazards and waste disposal tips 13.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled. Ignition temp.: 6°C MAK value: 20 ppm Extremely flammable. Health hazard upon inhalation 98 . Irreversible damage possible.: 95 °C Irritant for skin and eyes. Ignition temp. Potential teratogen. Ignition temp.: inflammable MAK value: 20 ppm Irritant for skin and eyes.

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mt. Routine operation including PQ. specification of the analytical requirements and purchase decision 2. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument.com For more information Mettler-Toledo AG. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. ©09/2009 Mettler-Toledo AG Printed in Switzerland. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. method validation. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. www. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators.e. ME-51725145A Markt Support AnaChem . Installation of the selected analytical system comprising IQ and OQ and training of personnel 3. Evaluation of the appropriate titration system (DQ) i. development of SOPs and maintenance of the validated state of the analytical system. Switzerland Tel. evaluation.